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EP0590539B1 - Verfahren zur Herstellung von Tetrathiafulvalen-Derivaten und ihrer Vorläufer - Google Patents

Verfahren zur Herstellung von Tetrathiafulvalen-Derivaten und ihrer Vorläufer Download PDF

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Publication number
EP0590539B1
EP0590539B1 EP93115470A EP93115470A EP0590539B1 EP 0590539 B1 EP0590539 B1 EP 0590539B1 EP 93115470 A EP93115470 A EP 93115470A EP 93115470 A EP93115470 A EP 93115470A EP 0590539 B1 EP0590539 B1 EP 0590539B1
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Prior art keywords
tetrathiafulvalene
dithiol
formula
tetrathiafulvalene derivative
precursor
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EP93115470A
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English (en)
French (fr)
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EP0590539A3 (de
EP0590539A2 (de
Inventor
Harald Dietmar c/o Osaka Works of Müller
Yoshinobu c/o Osaka Works of Ueba
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Sumitomo Electric Industries Ltd
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Sumitomo Electric Industries Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D339/00—Heterocyclic compounds containing rings having two sulfur atoms as the only ring hetero atoms
    • C07D339/02—Five-membered rings
    • C07D339/06—Five-membered rings having the hetero atoms in positions 1 and 3, e.g. cyclic dithiocarbonates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D497/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having oxygen and sulfur atoms as the only ring hetero atoms
    • C07D497/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having oxygen and sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D497/04—Ortho-condensed systems

Definitions

  • the present invention relates to a process for producing tetrathiafulvalene derivatives having specified structures, as well as to a process for producing precursors thereof having specified structures, which are useful as materials for the synthesis of organic charge-transfer complexes that are expected to be used in such applications as e.g. organic conductors, organic superconductors, organic magnetic substances, organic electrochromic materials and organic electroluminescence materials.
  • the above process (i) has some disadvantages in that the reducing reaction of carbon disulfide with an alkali metal is apt to cause explosion, the process generates reaction by-products which are difficult to be removed, it requires a number of steps including conversion of a 1,3-dithiol-2-thion derivative into a 1,3-dithiol-2-one derivative, and the yield of a tetrathiafulvalene derivative as the product of interest is poor.
  • the above process (ii) also has a problem of causing low product yield, because it requires a laborious removal of a phase-transfer catalyst. Especially, since a column chromatography is used for the removal of the phase-transfer catalyst, a prolonged time of labor is required and the productivity becomes poor, resulting in difficulty in scale up.
  • the above process (iii) has also disadvantages in that it requires 5 steps for the completion of the synthesis, thus entailing a poor yield, and it has a narrow application range because it can be applied to the synthesis of bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) as one of the tetrathiafulvalene derivatives but hardly to the synthesis of other tetrathiafulvalene derivatives.
  • BEDT-TTF bis(ethylenedithio)tetrathiafulvalene
  • the object of the present invention is to provide processes for the high yield production of high purity tetrathiafulvalene derivatives and their precursors which are useful for the development of new organic charge-transfer complexes, which can be applied to a broad range of tetrathiafulvalene derivatives and their precursors, and which are free from the danger of causing explosion, do not generate hardly removable reaction by-products and have high productivity due to the absence of a laborious removal of catalysts.
  • the present invention relates to a process for producing a tetrathiafulvalene derivative precursor represented by formula (1): wherein R 1 and R 2 may be the same or different and represent organic groups that may be linked together to form a ring, said process comprising the steps of:
  • Examples of the tetrathiafulvalene derivative precursor represented by formula (1) include those represented by any one of formulae (2) to (5):
  • the present invention also relates to a process for producing a tetrathiafulvalene derivative represented by formula (6): wherein R 1 and R 2 may be the same or different and represent organic groups that may be linked together to form a ring, the process comprising the steps of:
  • Examples of the tetrathiafulvalene derivative represented by formula (6) include those represented by any one of formulae (7) to (10):
  • Examples of the organic groups represented by R 1 and R 2 in formulae (1) and (6) include an alkyl group (e.g., methyl, ethyl), an aralkyl group (e.g., benzyl), a hydroxyalkyl group and a trimethylsilylethoxymethyl group.
  • examples thereof include an alkylene group (e.g., ethylene, propylene), a dimethylenethio group and a dimethylene ether group.
  • the present inventors have continued the studies further with the aim of finding a method for the selective one ring cleavage in 1,3,4,6-tetrathiapentalene-2,5-dione, and have found that one of the two rings can be cleaved selectively without generating hardly removable reaction by-products and with no danger of causing explosion, by a process in which an alkali metal alkoxide such as sodium methoxide is made into a solution of about 1 M in concentration by dissolving it in an alcohol such as methanol and, in an inert atmosphere free from e.g.
  • an alkali metal alkoxide such as sodium methoxide
  • the alkoxide solution is added to 1,3,4,6-tetrathiapentalene-2,5-dione and allowed to undergo the ring-opening reaction for about 10 minutes under a relatively low temperature condition of 30°C or below, especially at room temperature.
  • the process of the present invention for the production of tetrathiafulvalene derivatives and precursors thereof has been accomplished on the basis of such efforts.
  • one of the two rings of 1,3,4,6-tetrathiapentalene-2,5-dione (11) is selectively cleaved to obtain 1,3-dithiol-2-one-4,5-dithiolate dianion (12), which is subsequently allowed to react with a compound having a monovalent or divalent organic group that corresponds to R 1 and R 2 in formula (1).
  • a tetrathiafulvalene derivative precursor represented by formula (1) can be produced by a one-pot and one-step process without causing generation of hardly removable reaction by-products. Because of this, a tetrathiafulvalene derivative precursor can be produced in a high yield with a high purity in a short reaction time.
  • a tetrathiafulvalene derivative can be produced by employing the above precursor-producing step and a reaction step for the coupling of two molecules of the precursor, thereby rendering possible production of the tetrathiafulvalene derivative in a high yield with a high purity in a short reaction time.
  • the above production process also has an advantage of a broad application range, because not only various types of prior art tetrathiafulvalene derivatives and their precursors but also tetrathiafulvalene derivatives and their precursors which cannot be produced by the prior art process can be produced easily by the process of the present invention by selecting appropriate monovalent or divalent organic groups to be reacted with the 1,3-dithiol-2-one-4,5-dithiolate dianion (12).
  • one of the two rings of 1,3,4,6-tetrathiapentalene-2,5-dione represented by formula (11) as the starting material is selectively cleaved to obtain 1,3-dithiol-2-one-4,5-dithiolate dianion represented by formula (12).
  • the selective ring-opening reaction may be effected by a process in which an alkali metal alkoxide is made into a solution by dissolving it in the corresponding alcohol (e.g., NaOCH 3 in CH 3 OH, NaOC 2 H 5 in C 2 H 5 OH) and, in an inert atmosphere free from e.g.
  • an alkali metal alkoxide is made into a solution by dissolving it in the corresponding alcohol (e.g., NaOCH 3 in CH 3 OH, NaOC 2 H 5 in C 2 H 5 OH) and, in an inert atmosphere free from e.g.
  • 1,3,4,6-tetrathiapentalene-2,5-dione (11) is added to the alkoxide solution and allowed to undergo the ring-opening reaction for from 5 to 30 minutes, preferably from 5 to 20 minutes, more preferably from 8 to 12 minutes, under a relatively low temperature condition of 30°C or below, preferably from 15 to 30°C, more preferaby from 18 to 25°C, particularly preferably from 20 to 23°C, especially at room temperature.
  • a water-bath about 20°C
  • the concentration of the solution of an alkali metal alkoxide is generally about 1 M, preferably from 0.8 to 1.2 M, and more preferably from 0.95 to 1.05 M.
  • the amount of the alkali metal alkoxide is generally about 2 mol, preferably 1.8 to 2.2 mol, more preferably from 1.95 to 2.05 mol, per mol of 1,3,4,6-tetrathiapentalene-2,5-dione -2,5-dione (11).
  • room tempearture refers to such reaction conditions that external heating or cooling is not applied; in general the temperature range lies between from 20 to 25°C.
  • alkali metal alkoxide alkoxides of sodium and lower alcohols, such as sodium methoxide or sodium ethoxide may be used, as well as other alkoxides of various alkali metals and alcohols.
  • the alkoxide is generally used in an amount of 2 mols per 1 mol of 1,3,4,6-tetrathiapentalene-2,5-dione.
  • the product obtained after completion of the ring-opening reaction is next allowed to react with a compound containing a monovalent or divalent organic group which corresponds to R 1 and R 2 in formula (1) at room temperature for a period of from 1 to 30 hours, preferably from 2 to 10 hours, and more preferably from 2 to 4 hours.
  • the thus formed product is added to water and extracted with an organic solvent such as methylene chloride, and the solvent is removed under reduced pressure to obtain a crude product.
  • the crude product is subsequently purified by conventional means such as recrystallization or reprecipitation to obtain the tetrathiafulvalene derivative precursor represented by formula (1).
  • a halide such as a chloride, a bromide or an iodide may be used preferably as its reactivity with 1,3-dithiol-2-one-4,5-dithiolate dianion (12) is taken into consideration.
  • a monohalide is used when the organic group is monovalent, or a dihalide when the organic group is divalent.
  • a corresponding monohalide which includes: an alkyl halide such as alkyl chloride, alkyl bromide or alkyl iodide; an aralkyl halide such as aralkyl chloride, aralkyl bromide or aralkyl iodide; and a trimethylsilylethoxymethyl halide such as trimethylsilylethoxymethyl chloride, trimethylsilylethoxymethyl bromide or trimethylsilylethoxymethyl iodide.
  • the monohalide is generally used in an amount of about 2 mols per 1 mol of 1,3-dithiol-2-one-4,5-
  • a corresponding dihalide which includes: an alkylene dihalide such as alkylene dichloride, alkylene dibromide or alkylene diiodide (e.g., XCH 2 -(CH 2 ) n -CH 2 X, where X represents a halogen atom, and n represents an integer of 0 or more); and a dimethylenethiodihalide such as dimethylenethiodichloride, dimethylenethiodibromide or dimethylenethiodiiodide.
  • the dihalide is generally used in an amount of about 1 mol per 1 mol of 1,3-dithiol-2-one-4,5-dithiolate dianion.
  • tetrathiafulvalene derivative precursors represented by formula (1) which can be obtained by the above process for producing a tetrathiafulvalene derivative precursor
  • tetrathiafulvalene derivative precursors represented by formulae (2) to (5) are particularly useful as a starting material of the tetrathiafulvalene derivative and for the development of new organic charge-transfer complexes:
  • a predetermined amount of the tetrathiafulvalene derivative precursor thus produced by the aforementioned precursor production process is firstly dissolved or dispersed in a purified trialkyl phosphite which is selected from various compounds including triethyl phosphite.
  • the amount of the trialkyl phosphite to be used is not particularly limited but, in the case of triethyl phosphite for example, it is generally used in an amount of about 5 ml per one millimol of the tetrathiafulvalene derivative precursor.
  • the thus formed precipitate is recovered by filtration, washed with a solvent such as methanol, and then subjected to purification by conventional means such as recrystallization, reprecipitation, column chromatography or sublimation to obtain the tetrathiafulvalene derivative represented by formula (6).
  • tetrathiafulvalene derivatives represented by formula (6) which can be obtained by the above process for producing a tetrathiafulvalene derivative
  • tetrathiafulvalene derivatives represented by formulae (7) to (10) are compounds which renders possible development of new organic charge-transfer complexes:
  • tetrathiafulvalene derivative precursors can be produced by merely a one-pot and one-step reaction system which does not generate hardly removable by-products and is free from danger of causing explosion, but also tetrathiafulvalene derivatives can be produced from the tetrathiafulvalene derivative precursors by only a one-step reaction.
  • tetrathiafulvalene derivative precursors and tetrathiafulvalene derivatives having higher purity than those produced by the prior art process can be produced by safer reaction systems and with higher yields in comparison with the prior art process, thus rendering possible production of tetrathiafulvalene derivatives in a large scale with low cost that cannot be attained by the prior art process.
  • reaction solution was added to 150 ml of water, extracted three times with 50 ml of methylene chloride (CH 2 Cl 2 ) and dried on magnesium sulfate (MgSO 4 ), followed by removing the solvent under a reduced pressure to obtain a crude product in a solid form. Thereafter, the crude product was recrystallized from ethanol to obtain 0.7 g of a purified product with a yield of 70%.
  • CH 2 Cl 2 methylene chloride
  • MgSO 4 magnesium sulfate
  • a crude product of precursor was obtained in a solid form by repeating the process for the synthesis of tetrathiafulvalene derivative precursor I as in Example 1 above except that 1.22 g (9.6 mmol) of benzyl chloride was used instead of methyl iodide. Thereafter, the crude product was dissolved in methylene chloride and reprecipitated with pentane to obtain 1.44 g of a purified product with a yield of 85 to 90%.
  • a crude product of precursor was obtained in a solid form by repeating the process for the synthesis of tetrathiafulvalene derivative precursor I as in Example 1 above except that 1.6 g (9.6 mmol) of trimethylsilylethoxymethyl chloride was used instead of methyl iodide. Thereafter, the crude product thus prepared was subjected to purification by a column chromatography using a silica gel carrier and a hexane/ethyl acetate mixture solvent (80/20) to obtain 1.36 g (yield: 60%) of 4,5-bis(trimethylsilylethoxymethyl)thio-1,3-dithiol-2-one (molecular weight: 442.81) represented by formula (15):
  • a crude product of precursor was obtained in a solid form by repeating the process for the synthesis of tetrathiafulvalene derivative precursor I as in Example 1 above except that 0.9 g (4.8 mmol) of ethylene dibromide (1,2-dibromoethane) was used instead of methyl iodide. Thereafter, the crude product was recrystallized from ethanol to obtain 0.5 g of a purified product with a yield of 45 to 50%.
  • a crude product of precursor was obtained in a solid form by repeating the process for the synthesis of tetrathiafulvalene derivative precursor I as in Example 1 above except that 0.49 g (4.8 mmol) of propylene dibromide (1,3-dibromopropane) was used instead of methyl iodide. Thereafter, the crude product was recrystallized from ethanol to obtain 0.58 g of a purified product with a yield of 55%.
  • a crude product of precursor was obtained in a solid form by repeating the process for the synthesis of tetrathiafulvalene derivative precursor I as in Example 1 above except that 0.315 g (4.8 mmol) of dimethylenethiodichloride (bischloromethyl sulfide) was used instead of methyl iodide. Thereafter, the crude product was recrystallized from isopropyl alcohol to obtain 0.29 g of a purified product with a yield of 20 to 25%.
  • a crude product of precursor was obtained in a solid form by repeating the process for the synthesis of tetrathiafulvalene derivative precursor I as in Example 1 above except that 0.55 g (4.8 mmol) of dimethyleneoxydichloride (bischloromethyl ether) was used instead of methyl iodide. Thereafter, the crude product was recrystallized from isopropyl alcohol to obtain 0.5 g of a purified product with a yield of 50%.
  • a crude product of precursor was obtained in a solid form by repeating the process for the synthesis of tetrathiafulvalene derivative precursor I as in Example 1 above except that 0.56 g (4.8 mmol) of bromoethanol was used instead of methyl iodide. Thereafter, the crude product was recrystallized from isopropyl alcohol to obtain 0.71 g of a purified product with a yield of 55%.
  • Each of the tetrathiafulvalene derivatives and their precursors produced according to the present invention is useful for the development of new organic charge-transfer complexes.
  • tetrathiafulvalene derivative precursors can be produced by merely a one-pot and one-step reaction system which does not generates hardly removable by-products and is free from danger of e.g. causing explosion. Also, according to the process for the production of tetrathiafulvalene derivatives, tetrathiafulvalene derivatives can be produced from the tetrathiafulvalene derivative precursors by only a one-step reaction.
  • tetrathiafulvalene derivative precursors and tetrathiafulvalene derivatives having higher purity than those produced by the prior art process can be produced by safer reaction systems and with higher yields in comparison with the prior art process, thus rendering possible production of tetrathiafulvalene derivatives in a large scale with low cost that cannot be attained by the prior art process.
  • the production process of the present invention therefore, has a high industrial utilization value as a means for the low cost and large scale production of tetrathiafulvalene derivatives which are expected to be used in such applications as e.g. organic conductors, organic superconductors, organic magnetic substances, organic electrochromic materials and organic electroluminescence materials.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Heterocyclic Compounds Containing Sulfur Atoms (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)

Claims (2)

  1. Verfahren zur Herstellung eines Vorläufers für ein Tetrathiafulvalen-Derivat, dargestellt durch die Formel (1):
    Figure 00400001
    worin R1 und R2 gleich oder verschieden sein können und organische Gruppen bedeuten, die miteinander verbunden sein können, um einen Ring zu bilden, wobei das Verfahren die folgenden Schritte umfaßt:
    das Behandeln von 1,3,4,6-Tetrathiapentalen-2,5-dion bei einer Temperatur von 30°C oder weniger in einer alkoholischen Lösung, die ein Alkalimetallmethoxid enthält, in einer inerten Atmosphäre, um selektiv einen der Ringe des 1,3,4,6-Tetrathiapentalen-2,5-dions aufzuspalten und um ein 1,3-Dithiol-2-on-4,5-dithiolat-Dianion zu bilden, und
    das Umsetzen des 1,3-Ditniol-2-on-4,5-dithiolat-Dianions mit einer Verbindung mit einer organischen Gruppe, die den einwertigen organischen Gruppen, die durch R1 und R2 in Formel (1) dargestellt sind, oder der zweiwertigen organischen Gruppe, die durch R1 und R2 in Formel (1) gebildet wird, entspricht.
  2. Verfahren zur Herstellung eines Tetrathiafulvalen-Derivats, dargestellt durch die Formel (6):
    Figure 00400002
    worin R1 und R2 gleich oder verschieden sein können und organische Gruppen bedeuten, die miteinander verbunden sein können, um einen Ring zu bilden, wobei das Verfahren die folgenden Schritte umfaßt:
    das Behandeln von 1,3,4,6-Tetrathiapentalen-2,5-dion bei einer Temperatur von 30°C oder weniger in einer alkoholischen Lösung, die ein Alkalimetallmethoxid enthält, in einer inerten Atmosphäre, um selektiv einen der Ringe des 1,3,4,6-Tetrathiapentalen-2,5-dions aufzuspalten und um ein 1,3-Dithiol-2-on-4,5-dithiolat-Dianion zu bilden,
    das Umsetzen des 1,3-Dithiol-2-on-4,5-dithiolat-Dianions mit einer Verbindung mit einer organischen Gruppe, die den einwertigen organischen Gruppen, die durch R1 und R2 in Formel (6) dargestellt sind, oder der zweiwertigen organischen Gruppe, die durch R1 und R2 in Formel (6) gebildet wird, entspricht, und
    das Erwärmen und Rühren des Vorläufers für das Tetrathiafulvalen-Derivat in Gegenwart eines Trialkylphosphits, um eine Kupplungsreaktion zwischen zwei Molekülen des Vorläufers durchzuführen.
EP93115470A 1992-09-30 1993-09-24 Verfahren zur Herstellung von Tetrathiafulvalen-Derivaten und ihrer Vorläufer Expired - Lifetime EP0590539B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP262348/92 1992-09-30
JP4262348A JPH06107668A (ja) 1992-09-30 1992-09-30 テトラチアフルバレン誘導体前駆体、テトラチアフルバレン誘導体、テトラチアフルバレン誘導体前駆体の製造方法およびテトラチアフルバレン誘導体の製造方法

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EP0590539A2 EP0590539A2 (de) 1994-04-06
EP0590539A3 EP0590539A3 (de) 1994-04-13
EP0590539B1 true EP0590539B1 (de) 1999-05-12

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US (1) US5817837A (de)
EP (1) EP0590539B1 (de)
JP (1) JPH06107668A (de)
CA (1) CA2106794A1 (de)
DE (1) DE69324875T2 (de)
DK (1) DK0590539T3 (de)
RU (1) RU2122001C1 (de)

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JP2952346B2 (ja) * 1997-03-11 1999-09-27 東京商船大学長 ラングミュア・ブロジェット膜およびその製造方法
GB9712694D0 (en) * 1997-06-18 1997-08-20 British Nuclear Fuels Plc Improvements in and relating to compounds,sensors and extractants
US7038062B2 (en) * 2004-07-01 2006-05-02 The Goodyear Tire & Rubber Company Synthesis of cyclic trithiocarbonates from epoxides
JP5191701B2 (ja) * 2007-07-17 2013-05-08 株式会社エーピーアイ コーポレーション ジチアシクロペンテン誘導体またはジセレナシクロペンテン誘導体の製造方法
DE102008024186B3 (de) * 2008-05-19 2009-09-10 Siemens Aktiengesellschaft Elektrochrome Formulierung, Herstellungsverfahren dazu und elektrochromes organisches elektronisches Bauelement
KR101994262B1 (ko) * 2012-11-09 2019-06-28 삼성에스디아이 주식회사 리튬 이차 전지용 전해질 및 이를 포함하는 리튬 이차 전지

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US4089857A (en) * 1976-12-30 1978-05-16 International Business Machines Corporation Tetrathiapentalene and tetraselenapentalene compounds
US4111857A (en) * 1977-03-31 1978-09-05 International Business Machines Corporation Highly conducting organometallic polymers
US4405515A (en) * 1979-05-10 1983-09-20 International Business Machines Corporation Heterofulvalene geminal dithiolate compounds and their selenium and tellurium analogs and a method of fabricating the same
JPH0631219B2 (ja) * 1985-04-26 1994-04-27 味の素株式会社 フルバレン誘導体
FR2610928B1 (fr) * 1987-02-13 1989-05-05 Thomson Csf Composes organiques du type tetrathiafulvalene utilisables pour l'elaboration de films de langmuir-blodgett conducteurs et leur procede de fabrication
EP0408495B1 (de) * 1989-07-10 1994-04-13 Ciba-Geigy Ag Substituierte Tetrachalkogenfulvalene und Verfahren zu deren Herstellung
WO1991007397A1 (fr) * 1989-11-21 1991-05-30 Idemitsu Kosan Co., Ltd. Compose de thia- et/ou selenafulvalenyle

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EP0590539A3 (de) 1994-04-13
CA2106794A1 (en) 1994-03-31
US5817837A (en) 1998-10-06
DK0590539T3 (da) 1999-11-15
RU2122001C1 (ru) 1998-11-20
DE69324875D1 (de) 1999-06-17
DE69324875T2 (de) 1999-09-09
JPH06107668A (ja) 1994-04-19
EP0590539A2 (de) 1994-04-06

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